US20230020180A1 - Carrier foil-attached metal foil, method of manufacturing the same, and laminate including the same - Google Patents
Carrier foil-attached metal foil, method of manufacturing the same, and laminate including the same Download PDFInfo
- Publication number
- US20230020180A1 US20230020180A1 US17/779,955 US202017779955A US2023020180A1 US 20230020180 A1 US20230020180 A1 US 20230020180A1 US 202017779955 A US202017779955 A US 202017779955A US 2023020180 A1 US2023020180 A1 US 2023020180A1
- Authority
- US
- United States
- Prior art keywords
- foil
- carrier foil
- layer
- component
- metal foil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000011888 foil Substances 0.000 title claims abstract description 148
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 147
- 239000002184 metal Substances 0.000 title claims abstract description 147
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- 239000010410 layer Substances 0.000 claims description 143
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 86
- 239000000956 alloy Substances 0.000 claims description 66
- 229910045601 alloy Inorganic materials 0.000 claims description 66
- 239000012044 organic layer Substances 0.000 claims description 54
- 229910052759 nickel Inorganic materials 0.000 claims description 39
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 33
- 229910052750 molybdenum Inorganic materials 0.000 claims description 33
- 239000011733 molybdenum Substances 0.000 claims description 33
- 238000007747 plating Methods 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 24
- 150000001923 cyclic compounds Chemical class 0.000 claims description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- 229920005989 resin Polymers 0.000 claims description 14
- 239000011347 resin Substances 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 11
- 239000011572 manganese Substances 0.000 claims description 11
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims description 11
- 239000011574 phosphorus Substances 0.000 claims description 11
- NNRAOBUKHNZQFX-UHFFFAOYSA-N 2H-benzotriazole-4-thiol Chemical compound SC1=CC=CC2=C1NN=N2 NNRAOBUKHNZQFX-UHFFFAOYSA-N 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 9
- FXSVYLHRUWAOKB-UHFFFAOYSA-N SC1=CC=CC=2NN=NC21.[Na] Chemical compound SC1=CC=CC=2NN=NC21.[Na] FXSVYLHRUWAOKB-UHFFFAOYSA-N 0.000 claims description 8
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 8
- 239000012964 benzotriazole Substances 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 claims description 5
- AFBBKYQYNPNMAT-UHFFFAOYSA-N 1h-1,2,4-triazol-1-ium-3-thiolate Chemical compound SC=1N=CNN=1 AFBBKYQYNPNMAT-UHFFFAOYSA-N 0.000 claims description 5
- FTERHQFTRLXWDG-UHFFFAOYSA-N 2-methyl-1h-1,2,4-triazole-5-thione Chemical compound CN1C=NC(S)=N1 FTERHQFTRLXWDG-UHFFFAOYSA-N 0.000 claims description 5
- WZUUZPAYWFIBDF-UHFFFAOYSA-N 5-amino-1,2-dihydro-1,2,4-triazole-3-thione Chemical compound NC1=NNC(S)=N1 WZUUZPAYWFIBDF-UHFFFAOYSA-N 0.000 claims description 5
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 claims description 4
- GTODOEDLCNTSLG-UHFFFAOYSA-N 2h-triazole-4-carboxylic acid Chemical compound OC(=O)C1=CNN=N1 GTODOEDLCNTSLG-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 abstract description 7
- 230000007547 defect Effects 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 16
- 238000009713 electroplating Methods 0.000 description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 11
- 229910052708 sodium Inorganic materials 0.000 description 11
- 239000011734 sodium Substances 0.000 description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 238000007788 roughening Methods 0.000 description 8
- 239000012535 impurity Substances 0.000 description 7
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 239000004734 Polyphenylene sulfide Substances 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 229920000069 polyphenylene sulfide Polymers 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000007772 electroless plating Methods 0.000 description 3
- 229930185605 Bisphenol Natural products 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000004843 novolac epoxy resin Substances 0.000 description 2
- -1 polyethylene terephthalate Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 101150059448 cdk7 gene Proteins 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Images
Classifications
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- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1635—Composition of the substrate
- C23C18/1637—Composition of the substrate metallic substrate
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
- C23C18/1651—Two or more layers only obtained by electroless plating
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
- C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/03—Conductive materials
- H05K2201/0332—Structure of the conductor
- H05K2201/0335—Layered conductors or foils
- H05K2201/0355—Metal foils
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
- H05K3/025—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates by transfer of thin metal foil formed on a temporary carrier, e.g. peel-apart copper
Definitions
- the present invention relates to a carrier foil-attached metal foil, a method of manufacturing the same, and a laminate for forming a printed circuit board including the metal foil.
- a printed circuit board having a high-density ultra-fine wiring pattern is required.
- Such a printed circuit board may be manufactured by forming the high-density ultra-fine wiring pattern on a metal foil included in the printed circuit board.
- a relatively thin metal foil e.g., a metal foil having a thickness of 9 ⁇ m or less
- the metal foil may be easily wrinkled or bent during the manufacturing of the printed circuit board.
- a carrier foil-attached metal foil in which a carrier foil is attached to one surface of the metal foil through a release layer has been used.
- a basic structure of the printed circuit board is formed by peeling the release layer and the carrier foil from the carrier foil-attached metal foil.
- peeling the release layer and the carrier foil if the metal foil is deformed or impurities remain on the metal foil, a defect rate of the printed circuit board increases. Accordingly, it is required to stabilize a peeling strength when peeling the release layer and the carrier foil so that the impurities do not remain on the metal foil while preventing the deformation of the metal foil.
- the present invention provides a carrier foil-attached metal foil capable of minimizing a deformation of a metal foil and impurities remaining on the metal foil when peeling the carrier foil from the metal foil.
- the present invention provides a method of manufacturing the carrier foil-attached metal foil.
- the present invention provides a laminate for forming a printed circuit board with excellent reliability by including the carrier foil-attached metal foil.
- an carrier foil-attached metal foil including: a carrier foil; an alloy layer provided on the carrier foil; an organic layer provided on the alloy layer; and a metal layer provided on the organic layer, in which the alloy layer includes a first component containing nickel (Ni) and a second component containing molybdenum (Mo), and a ratio a:b of the first component a and the second component b is a weight ratio of 40 to 80:60 to 20, and the organic layer includes a cyclic compound containing two or more nitrogen atoms.
- a method of manufacturing a carrier foil-attached metal foil including: preparing a carrier foil; forming an alloy layer on the carrier foil; forming an organic layer on the alloy layer; and forming a metal layer on the organic layer, in which the alloy layer is formed of a plating solution including a first component containing nickel (Ni) and a second component containing molybdenum (Mo), and a ratio a:b of the first component a and the second component b is a weight ratio of 40 to 80:60 to 20, and the organic layer is formed of a coating solution including a cyclic compound containing two or more nitrogen atoms.
- a laminate including: the carrier foil-attached metal foil; and a resin substrate provided on the carrier foil-attached metal foil.
- a carrier foil-attached metal foil includes an alloy layer containing molybdenum and nickel at a specific ratio and a release layer formed of an organic layer containing a cyclic compound containing two or more nitrogen atoms, when peeling the carrier foil from the metal foil, it is possible to prevent impurities (e.g., metal components derived from the alloy layer) from remaining on the metal foil while minimizing a deformation of the metal foil.
- impurities e.g., metal components derived from the alloy layer
- a laminate for forming a printed circuit board according to the present invention includes the carrier foil-attached metal foil, a defect rate is minimized, and thus the present invention may provide a laminate for forming a printed circuit board with excellent reliability.
- FIG. 1 is a cross-sectional view of a carrier foil-attached metal foil according to the present invention.
- the present invention is to provide a carrier foil-attached metal foil having a specific composition and structure of an alloy layer and an organic layer serving as a release layer.
- the present invention relates to a carrier foil-attached metal foil capable of maintaining an alloy layer and an organic layer, which are bonded to a carrier foil, at an appropriate bonding strength (peeling strength) before peeling the alloy layer and the organic layer from a metal layer, minimizing a deformation of the metal layer by smoothly peeling the alloy layer and the organic layer from the metal layer when peeling, and preventing impurities from remaining in the metal layer after peeling, a method of manufacturing the carrier foil-attached metal foil, and a laminate including the carrier foil-attached metal foil, which will be described in detail as follows.
- a carrier foil-attached metal foil according to the present invention includes a carrier foil, an alloy layer, an organic layer, and a metal layer, which will be described in detail with reference to FIG. 1 as follows.
- a carrier foil 10 included in the carrier foil-attached metal foil according to the present invention may serve as a support layer to prevent a deformation of the metal layer 40 during movement or use of the carrier foil-attached metal foil.
- the carrier foil 10 may be made of a metal such as copper or aluminum; or a polymer such as polyethylene terephthalate (PET), polyphenylene sulfide (PPS), or Teflon.
- a thickness of the carrier foil 10 may be 10 to 50 ⁇ m. As the thickness of the carrier foil 10 is within the above range, it is possible to prevent the carrier foil-attached metal foil from becoming thicker than necessary while smoothly performing the role of a support layer.
- the alloy layer 20 included in the carrier foil-attached metal foil according to the present invention is a first release layer provided on the carrier foil 10 , and may serve to bond the carrier foil 10 and the organic layer 30 and prevent a component of the carrier foil 10 from being diffused into the metal layer 40 .
- the alloy layer 20 may include a first component containing nickel (Ni) and a second component containing molybdenum (Mo).
- the first component is nickel, and may prevent the component of the carrier foil 10 from being diffused and adsorbed into the metal layer 40 as the nickel is contained in the alloy layer 20 .
- the second component is molybdenum, and provides a site to which a cyclic compound included in the organic layer 30 is bonded as the molybdenum is contained in the alloy layer 20 , thereby providing a required bonding strength (peeling strength) between the alloy layer 20 and the organic layer 30 .
- a ratio a:b of the first component a and the second component b may be within 40 to 80:60 to 20, and specifically, a weight ratio of 60 to 80:40 to 20.
- the component of the carrier foil 10 may be prevented from being diffused into the metal layer 40 , and thus, may peel the carrier foil 10 so that impurities do not remain in the metal layer 40 , and may provide the required bonding strength (peeling strength) before and after peeling to the alloy layer 20 .
- peeling strength peeling strength
- the bonding strength (peeling strength) between the carrier foil 10 , the alloy layer 20 , and the organic layer 30 is maintained stably, so the carrier foil 10 may be peeled well.
- the alloy layer 20 may further include a third component containing at least one selected from the group consisting of cobalt (Co), phosphorus (P), manganese (Mn), and iron (Fe).
- the bonding strength (peeling strength) between the alloy layer 20 and the organic layer 30 may be increased, and even when the carrier foil-attached metal foil is heat-treated at 200° C. or higher, the bonding strength (peeling strength) may be stably maintained.
- the alloy layer 20 further includes a third component c
- a ratio a:b:c of the first component a, the second component b, and the third component c may be a weight ratio of 30 to 60:25 to 50:1 to 40.
- a thickness of such an alloy layer 20 may be 30 nm to 1 ⁇ m. As the thickness of the alloy layer 20 is within the above range, the required bonding strength (peeling strength) may be exhibited while the alloy layer 20 and the organic layer 30 are stably bonded.
- the organic layer 30 included in the carrier foil-attached metal foil according to the present invention is a second release layer provided on the alloy layer 20 , and may serve to bond the alloy layer 20 and the metal layer 40 and prevent the component of the carrier foil 10 and the component of the alloy layer 20 from being diffused into the metal layer 40 .
- the organic layer 30 may include a cyclic compound containing two or more nitrogen atoms.
- the cyclic compound may be at least one selected from the group consisting of benzotriazole, mercapto benzimidazole, mercapto benzotriazole, sodium mercapto benzotriazole, 3-amino-5-mercapto-1,2,4-triazole, 3-mercapto-1,2,4-triazole, triazole-5-carboxylic acid, 1-methyl-3-mercapto-1,2,4-triazole, and 1-phenyl-5-mercapto tetrazole.
- the cyclic compound included in the organic layer 30 may be sodium mercapto benzotriazole, mercapto benzotriazole, 3-amino-5-mercapto-1,2,4-triazole, 3-mercapto-1,2,4-triazole, 1-methyl-3-mercapto-1,2,4-triazole, or 1-phenyl-5-mercapto tetrazole to which a mercapto group (—SH) (high bonding strength with a nitrogen atom due to many unshared electron pairs) and 3 or more nitrogen atoms are bonded.
- —SH mercapto group
- the structure of the organic layer 30 may be stably maintained, thereby preventing the component of the carrier foil 10 or the component of the alloy layer 20 from being diffused and absorbed into the metal layer 40 .
- a thickness of the organic layer 30 may be 1 to 50 nm. As the thickness of the organic layer 30 is within the above range, the required bonding strength (peeling strength) may be exhibited while the organic layer 30 and the metal layer 40 are stably bonded.
- the metal layer 40 included in the carrier foil-attached metal foil according to the present invention may serve as a circuit layer by going through the process of forming a wiring pattern in a process of manufacturing a printed wiring board.
- the metal layer 40 may be made of copper.
- a thickness of the metal layer 40 may be 0.1 to 5 As the thickness of the metal layer 40 is within the above range, it is possible to implement a high-density ultra-fine wiring pattern while preventing micropores from being generated.
- a bonding strength (peeling strength) S 1 between the carrier foil 10 and the alloy layer 20 and a bonding strength (peeling strength) S 2 between the alloy layer 20 and the organic layer 30 may be equal, which may be greater than a bonding strength (peeling strength) S 3 between the organic layer and the metal layer 40 (S 1 , S 2 >S 3 ).
- the bonding strength (peeling strength) S 3 between the organic layer 30 and the metal layer 40 may be 2 to 20 gf/cm, and specifically 5 to 15 gf/cm.
- the carrier foil-attached metal foil according to the present invention may further include a surface roughening layer 50 provided on the metal layer 40 .
- the surface roughening layer 50 may serve to increase the bonding strength between the carrier foil-attached metal foil and the resin substrate when manufacturing a laminate by bonding the carrier foil-attached metal foil and the resin substrate.
- the surface roughening layer 50 may include copper.
- the surface roughening layer 50 may include a seed layer having a thickness of 0.5 to 1 ⁇ m and a cover layer having a thickness of 1.0 to 2.0 ⁇ m.
- Such a surface roughening layer 50 may have an arithmetic mean roughness Ra of 0.2 to 0.3 ⁇ m, and a ten-point average roughness Rz of 1.5 to 2.5 ⁇ m. As the roughness of the surface roughening layer 50 is within the above range, the high bonding strength between the carrier foil-attached metal foil and the resin substrate may be exhibited.
- the carrier foil-attached metal foil according to the present invention may further include a diffusion barrier layer (not illustrated) provided between the carrier foil 10 and the alloy layer 20 .
- the diffusion barrier layer may include nickel and phosphorus.
- the carrier foil-attached metal foil according to the present invention may further include an antioxidant layer (not illustrated) provided between the organic layer 30 and the metal layer 40 .
- the antioxidant layer may include nickel and phosphorus.
- the present invention provides a method of manufacturing a carrier foil-attached metal foil, which will be described in detail as follows.
- a carrier foil is prepared. Specifically, a metal foil film made of copper or aluminum; or a polymer thin film made of polyethylene terephthalate (PET), polyphenylene sulfide (PPS), or Teflon may be prepared as a carrier foil.
- PET polyethylene terephthalate
- PPS polyphenylene sulfide
- Teflon Teflon
- the alloy layer is formed on the prepared carrier foil.
- the alloy layer may be formed by electroplating or electroless plating.
- a plating solution including a first component containing nickel (Ni) and a second component containing molybdenum (Mo) may be used.
- a ratio a:b of a first component a and a second component b may be a weight ratio of 40 to 80:60 to 20.
- the carrier foil, the alloy layer, and the organic layer may be well bonded to prevent the component of the carrier foil from being diffused into the metal layer.
- the plating solution may further include a third component containing at least one selected from the group consisting of cobalt (Co), phosphorus (P), manganese (Mn), and iron (Fe).
- a third component containing at least one selected from the group consisting of cobalt (Co), phosphorus (P), manganese (Mn), and iron (Fe).
- the organic layer is formed by a coating method such as an immersion method, a showering method, or a spray method.
- a coating solution including a cyclic compound containing two or more nitrogen atoms may be used.
- the cyclic compound may be at least one selected from the group consisting of benzotriazole, mercapto benzimidazole, mercapto benzotriazole, sodium mercapto benzotriazole, 3-amino-5-mercapto-1,2,4-triazole, 3-mercapto-1,2,4-triazole, triazole-5-carboxylic acid, 1-methyl-3-mercapto-1,2,4-triazole, and 1-phenyl-5-mercapto tetrazole.
- the cyclic compound may be sodium mercapto benzotriazole, mercapto benzotriazole, 3-amino-5-mercapto-1,2,4-triazole, 3-mercapto-1,2,4-triazole, 1-methyl-3-mercapto-1,2,4-triazole, or 1-phenyl-5-mercapto tetrazole, to which a mercapto group (—SH) (high bonding strength with a nitrogen atom due to many unshared electron pairs) and 3 or more nitrogen atoms are bonded.
- —SH mercapto group
- the content of this cyclic compound may be 0.1 to 2 parts by weight based on 100 parts by weight of the coating solution. As the content of the cyclic compound is within the above range, the amount of the cyclic compound adsorbed into the metal layer is optimized, thereby preventing an appearance from being deteriorated while increasing bonding strength (peeling strength).
- the metal layer is formed by a plating method such as electroplating or electroless plating; or a deposition method such as chemical vapor deposition (CVC), physical chemical vapor deposition (PVC), or ion plating.
- a plating method such as electroplating or electroless plating
- a deposition method such as chemical vapor deposition (CVC), physical chemical vapor deposition (PVC), or ion plating.
- the method of manufacturing a carrier foil-attached metal foil according to the present invention may further include forming a surface roughening layer on the metal layer.
- the surface roughening layer may be formed by going through a process of primary electroplating (forming a seed layer) and secondary electroplating (forming a cover layer).
- the primary electroplating may be performed using an electroplating solution containing 60 to 70 g/L of copper and 150 to 170 g/L of sulfuric acid under conditions of a temperature of 25° C. and a current density of 15 ASD.
- the secondary electroplating may be performed using an electroplating solution containing 220 to 240 g/L of copper and 120 to 140 g/L of sulfuric acid under conditions of a temperature of 45° C. and a current density of 15 ASD.
- the method of manufacturing a carrier foil-attached metal foil according to the present invention may further include forming a diffusion barrier layer between the carrier foil and the alloy layer.
- the method of manufacturing a carrier foil-attached metal foil according to the present invention may further include forming an antioxidant layer between the organic layer 30 and the metal layer 40 .
- the present invention provides a laminate including a carrier foil-attached metal foil and a resin substrate.
- the carrier foil-attached metal foil included in the laminate according to the present invention may serve as a circuit layer on which a wiring pattern is formed.
- the description of this carrier foil-attached metal foil is the same as described above, and therefore, will be omitted.
- the resin substrate included in the laminate according to the present invention serves as an insulating layer.
- the resin substrate is commonly known and may have a structure in which inorganic or organic fibers are impregnated with resin.
- the resin may be at least one selected from the group consisting of naphthalene-based epoxy resins, bisphenol A-type epoxy resins, phenol novolac epoxy resins, cresol novolac epoxy resins, rubber-modified epoxy resins, phosphorus-based epoxy resins, and bisphenol F-type epoxy resins.
- the laminate according to the present invention is a laminate for forming a printed circuit board, and as the laminate includes the above-described carrier foil-attached metal foil, a defect rate is minimized, so the laminate may be used as a laminate for forming a printed circuit board with excellent reliability.
- a carrier foil formed of a copper foil having a thickness of 18 ⁇ m was immersed in 5 wt % of sulfuric acid, pickled, and then washed with pure water.
- the electroplating was performed at 5 A/dm 2 for 30 seconds while maintaining pH 10 or higher.
- the carrier foil on which the alloy layer is formed was washed, and then, was immersed for 30 seconds in a coating solution of 30° C. which contains 1 part by weight of sodium mercapto benzotriazole and 99 parts by weight of pure water to form an organic layer having a thickness of 1 to 10 nm on the alloy layer.
- the carrier foil on which the alloy layer and the organic layer were formed was washed, and then, electroplated to form a metal layer (electrolytic copper layer) having a thickness of 2 ⁇ m to manufacture the carrier foil-attached metal foil.
- a copper sulfate solution of 23° C. having a copper concentration of 150 g/L and a free sulfuric acid concentration of 100 g/L was used for the electroplating, and a current density was 5 A/dm 2 .
- a carrier foil-attached metal foil was manufactured in the same process as in Example 1, except that benzotriazole was used instead of sodium mercapto benzotriazole when forming an organic layer.
- a carrier foil-attached metal foil was manufactured in the same process as in Example 1, except that mercapto benzimidazol was used instead of sodium mercapto benzotriazole when forming an organic layer.
- a carrier foil-attached metal foil was manufactured in the same process as in Example 1, except that an alloy layer was formed by adjusting a plating solution composition so that a ratio of nickel:molybdenum was a weight ratio of 80:20.
- a carrier foil-attached metal foil was manufactured in the same process as in Example 1, except that an alloy layer was formed by adjusting a plating solution composition so that a ratio of nickel:molybdenum was a weight ratio of 40:60.
- a carrier foil-attached metal foil was manufactured in the same process as in Example 1, except that an organic layer was not formed.
- a carrier foil-attached metal foil was manufactured in the same process as in Example 1, except that an alloy layer was formed by adjusting a plating solution composition so that a ratio of nickel:molybdenum was a weight ratio of 85:15.
- a carrier foil-attached metal foil was manufactured in the same process as in Example 1, except that an alloy layer was formed by adjusting a plating solution composition so that a ratio of nickel:molybdenum was a weight ratio of 35:65.
- the ratio of nickel:molybdenum was a weight ratio of 35:65
- the electroplating was not performed well, so the alloy layer was not properly formed.
- the bonding strength between the subsequently formed organic layer and the metal layer was low, making it difficult to use as the carrier foil-attached metal foil.
- a laminate was manufactured by forming a resin substrate (Doosan Electronics prepreg (DS-7409HG)) laminated on the carrier foil-attached metal foil manufactured in Examples 1 to 9 and Comparative Examples 1 to 5 and then pressing the resin substrate at a pressure of 220 MPa at 220° C. for 100 minutes.
- a resin substrate Doosan Electronics prepreg (DS-7409HG)
- the peeling strength (gf/cm) of the carrier foil-attached metal foil manufactured in Examples 1 to 9 and Comparative Examples 1 to 5 and the laminate manufactured in Manufacturing Examples 1 to 9 and Comparative Manufacturing Examples 1 to 5 was measured by IPC-TM-650 standard (using a plate-shaped test piece having width of 10 mm ⁇ length of 10 cm), and the results were shown in Table 1 below.
- the peeling strength means the peeling strength between the metal layer and the structure in which the organic layer/alloy layer/carrier foil are bonded.
- the carrier foil-attached metal foil (Examples 1 to 9) of Manufacturing Examples 1 to 9 according to the present invention maintained the bonding with the carrier foil due to the alloy layer and organic layer, and then, was peeled well, but it was confirmed that the carrier foil-attached metal foil of Comparative Manufacturing Examples 1 to 4 was not peeled. In addition, it was confirmed that the carrier foil-attached metal foil of Comparative Manufacturing Example 5 was pressed and then not easily peeled due to high peeling strength.
- the component of the alloy layer (nickel) does not remain (nickel residue 0%) on the surface of the metal layer after peeling, but in the carrier foil-attached metal foil of Comparative Example 1, it was confirmed that a large amount of the component of the alloy layer (nickel) remains on the surface of the metal layer after peeling (nickel residue 5.08%).
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Applications Claiming Priority (3)
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KR1020190154286A KR102137068B1 (ko) | 2019-11-27 | 2019-11-27 | 캐리어박 부착 금속박, 이의 제조방법 및 이를 포함하는 적층체 |
KR10-2019-0154286 | 2019-11-27 | ||
PCT/KR2020/014066 WO2021107397A1 (ko) | 2019-11-27 | 2020-10-15 | 캐리어박 부착 금속박, 이의 제조방법 및 이를 포함하는 적층체 |
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US (1) | US20230020180A1 (ko) |
EP (1) | EP4050128A4 (ko) |
JP (1) | JP2023504808A (ko) |
KR (1) | KR102137068B1 (ko) |
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KR102137068B1 (ko) * | 2019-11-27 | 2020-07-23 | 와이엠티 주식회사 | 캐리어박 부착 금속박, 이의 제조방법 및 이를 포함하는 적층체 |
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- 2019-11-27 KR KR1020190154286A patent/KR102137068B1/ko active IP Right Grant
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- 2020-10-15 CN CN202080094784.2A patent/CN115023514A/zh active Pending
- 2020-10-15 WO PCT/KR2020/014066 patent/WO2021107397A1/ko unknown
- 2020-10-15 EP EP20894258.1A patent/EP4050128A4/en active Pending
- 2020-10-15 US US17/779,955 patent/US20230020180A1/en active Pending
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WO2015170715A1 (ja) * | 2014-05-07 | 2015-11-12 | 三井金属鉱業株式会社 | キャリア付銅箔、キャリア付銅箔の製造方法、キャリア付銅箔を用いて得られる銅張積層板及びプリント配線板 |
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EP4050128A4 (en) | 2023-12-27 |
KR102137068B1 (ko) | 2020-07-23 |
JP2023504808A (ja) | 2023-02-07 |
EP4050128A1 (en) | 2022-08-31 |
CN115023514A (zh) | 2022-09-06 |
WO2021107397A1 (ko) | 2021-06-03 |
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